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Dilute sulfuric acid hydrolysis of tropical region biomass

Article  in  Journal of Renewable and Sustainable Energy · March 2012


DOI: 10.1063/1.3663878

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JOURNAL OF RENEWABLE AND SUSTAINABLE ENERGY 4, 021201 (2012)

Dilute sulfuric acid hydrolysis of tropical region biomass


I. P. Hernández,a) José A. Pérez-Pimienta, Sarah Messina,
and Claudia E. Saldaña Durán
Ingenierı́a Quı́mica—Universidad Autónoma de Nayarit, Avenida de la Cultura s/n,
c.p. 63190, Edificio E2, Nayarit 63155, Mexico
(Received 3 February 2011; accepted 28 October 2011; published online 16 March 2012)

Although ethanol can be produced from a wide range of biomass materials,


biomass, from the tropical region, like mango (skin or bagasse) is a crop residue
readily available today as a non-conventional crop for the saccharification process
that has had little attention. It has the benefits to be found in large quantities and in
an industrial level is completely separated into its components with a free access for
acid or enzymatic hydrolysis. These agro-industrial waste as well as other materials
like sugarcane bagasse and pine wood are abundant enough, and in virtue of their
high carbohydrate content hold tremendous potential for large-scale bioethanol
production. The objective of this work is to develop a comparative analysis using
dilute acid hydrolysis process between mango (skin and bagasse), sugarcane
bagasse, and pine wood. The biomass was subjected to pretreatments like alkaline
hydrolysis using calcium sulfate and sodium hydroxide, water immersion, and water
autoclaved at 121  C. Experimental results showed that the maximum percentages
of sugar recovery were for sugarcane bagasse—56.62%, pine wood—82.36%,
mango skin—97.37%, and mango bagasse—202.91%. From the tested biomass
materials, only mango bagasse has a considerable fraction of already digestible
sugar that does not undergo a pretreatment þ hydrolysis process. V C 2012 American

Institute of Physics. [doi:10.1063/1.3663878]

I. INTRODUCTION
Ethanol can be produced from renewable resources such as agricultural waste or forestry
waste.1 In addition, the conversion of cellulosic materials into ethanol requires no energy input
from fossil fuels. Lignin, which is a by-product, can be burned to provide the energy required.
The carbon dioxide released during the production and the use of ethanol can be converted
back to biomass in the cultivation of energy crops (cellulosic materials) to provide new raw
material for the production.2 Consequently, the contribution to the content of greenhouse gases
is negligible. Raw material such as lignocelluloses can be considered as an infinite resource.
Another advantage gained by using ethanol as fuel is the reduction in hydrocarbon emissions.1
Mango is one of the most important tropical fruits accounting for nearly 50% of total with
a global production estimated by The Food and Agriculture Organization of the United Nations
(FAO) of 30.7 million tons during 2010. As mango is a seasonal fruit, it is processed into vari-
ous products, and during its processing, huge amount of peel and bagasse (composed by fibers,
peel, and pulp) is generated as a by-product, and its disposal is a major problem. The peel con-
stitutes about 15%–20% of the fresh fruit, which is mainly composed of cellulose, hemicellu-
lose, and lignin. These agro-industrial waste from other materials such as sugarcane bagasse
and pine wood are abundant enough and, in virtue of their high carbohydrate content, hold tre-
mendous potential for large-scale bioethanol production in which the mango peel and bagasse
could be an excellent feedstock from the tropical region that have had little attention, with the
benefits to be found in large quantities and in an industrial level (e.g., concentrate fruit plants)

a)
Electronic mail: paz.rosales@gmail.com. Tel.: (52)-311-211-8821.

1941-7012/2012/4(2)/021201/9/$30.00 4, 021201-1 C 2012 American Institute of Physics


V

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021201-2 Hernández et al. J. Renewable Sustainable Energy 4, 021201 (2012)

are completely separated from all the other components with a free access for acid or enzymatic
hydrolysis.3,4
A number of processes for hydrolyzing cellulose into glucose have been developed over
the years. The vast majority of processing schemes utilizes either cellulolytic enzymes or sulfu-
ric acid of varying concentration. Historically, enzymes have been too expensive for economi-
cal production of fuel ethanol from biomass.5 Acid hydrolysis leads to fission of the glycosidic
bonds and occurs in three stages: first, the proton of the acid catalyst interacts rapidly with the
glycosidic oxygen that bonds two sugar units, forming the so called conjugated acid; second,
there is a slow cleavage of the C-O bond, resulting in an intermediate cation of cyclic carbon;
third, the carbon cation starts a rapid addition of a water molecule, resulting in a stable final
product and in the proton release.6
Dilute sulfuric acid hydrolysis is a chemical hydrolysis for either the pretreatment before
enzymatic hydrolysis or the conversion of lignocellulose to the corresponding sugars. In dilute
acid hydrolysis, the hemicellulose fraction is depolymerized at lower temperature than the cel-
lulose fraction. If higher temperature or longer retention times are applied, the formed monosac-
charides will be further hydrolyzed to other compounds. It is therefore suggested that the hydro-
lysis process be carried out in at least two stages, the first stage at relatively milder conditions
during which the hemicellulose fraction is hydrolyzed and a second stage can be carried out by
enzymatic hydrolysis or dilute acid hydrolysis at higher temperatures during which the cellulose
is hydrolyzed.7
High reaction rates (compared with enzymatic process), low acid consumption, and low
cost of sulfuric acid (compared with base-catalyzed pretreatments) are some of the advantages
of the dilute sulfuric acid pretreatment.8 Avoiding degradation of monosaccharides is important
not only to improve the yield of hydrolysis but also to avoid the problems associated with the
inhibition of sugars fermentation to ethanol.9 The most accepted model considers that the hemi-
cellulose decomposition occurs in two stages. First, the hemicellulose chain is decomposed into
xylo-oligosaccharides and second into xylose monomers.6 The most important inhibitors are
furans, carboxylic acids, and phenolics compounds. Furfural and 5-hydro-xymethyl furfural
(HMF) are the most important furans. They are formed by decomposition of pentoses and hexo-
ses, respectively. Acetic acid is formed from hydrolysis of the acetyl groups in the hemicellu-
lose, as a consequence of deacetylation of acetylated pentosan.6,7
The hemicellulose fraction can be easily extracted and hydrolyzed by dilute acid treatment.
Alkaline treatment digests the lignin matrix and makes cellulose and hemicellulose available to
enzyme degradation. Alternatively, biological delignification of agricultural residues is possible
using selected strains of Panus tigrinus, a white rot fungus.10 Also, the swelling of the cellu-
losic material has been demonstrated as an effective pretreatment to increase the possibility of
attach of chemical compounds to monomerics carbohydrates in their structure, increasing the
accessible surface area.11
Lignocellulosic materials and hydrolyses processes are very complicated. Factors influenc-
ing the yields of the lignocellulose to the monomeric sugars and the by-products are, e.g., parti-
cle size, liquid to solid ratio, type and concentration of acid used, temperature, and reaction
time, as well as the length of the macromolecules, degree of polymerization of cellulose,
configuration of the cellulose chain, association of cellulose with other protective polymeric
structures within the plant cell wall such as lignin, pectin, hemicellulose, proteins, and mineral
elements.12 However, since these variables are not identical in different types of lignocellulosic
materials, it would be difficult to extent the data on a type of lignocellulose to another as well
to test pretreatment sequences to obtain an improvement in the overall efficiency using the
dilute acid process alone or in combination.13
The present study develop a comparative analysis using dilute acid hydrolysis processes
between mango (skin and bagasse), sugarcane bagasse, and pine wood with the effect of some
hydrolysis parameters in production of monomerics sugars using sulfuric acid. The variables
considered were the effects of hydrolysis temperature, time, and acid concentration. Also, the
biomass was subjected to pretreatments such as alkaline hydrolysis using calcium sulfate and
sodium hydroxide, and water immersion for a period of time, and water autoclaved at 121  C.

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021201-3 Cellulosic materials J. Renewable Sustainable Energy 4, 021201 (2012)

Hydrolysis of biomass resulted in percentage of sugar recovery reported and compared with the
data obtained through identical experimental designs and statistical analysis techniques of all
cellulosic feedstock.

II. METHODOLOGY
A. Cellulosic materials
All biomass used in all the experiments were obtained in southwest Mexico; sugarcane ba-
gasse was supplied from the sugar plant Ingenio El Molino de Menchaca (Tepic, Nayarit) as a
byproduct of sugar production. The mango skin and bagasse were obtained as a byproduct of a
local production company of fruit concentrates (MexiFrutas). Finally, pine sawdust was
obtained from a local sawmill (Tepic, Nayarit), which was used as test material. All materials
received the same treatment, were dried at 45 6 5  C for 2 days to less of 10% moisture before
use, partly knife-milled and screened having particle size between 10 mesh and 35 mesh
(0.5 mm and 2.0 mm) for uniformity, and the moisture of the material was determined by a
moisture analyzer IR-200 (Denver instrument Co., Denver, USA) dry scale (105  C, 20 min).
The ground and screened biomass samples were stored in seal plastic bags at room temperature,
prior to hydrolysis. All experiments were carried out with a minimum of three replicates, and
the mean values are reported.

B. Dilute acid hydrolysis


The dilute acid hydrolysis was executed according to the methods and specification of
those used with other lignocelluloses substrates.14–16 Three hot plate stirrers were utilized for
these experiments heated in a reflux system. The operation variables examined were (a) hydro-
lysis retention time (0–300 min), and (b) acid concentration of 1–5% (w/w) H2SO4; in a 1/10
relation (dry weight/dilute acid volume) with a speed of agitation of 250 rpm and constant tem-
perature of 100  C. The focus of the experiments included the analysis of all cellulosic materi-
als to evaluate, which is performed in triplicate. Time zero of all reactions corresponded with
biomass injection. The experimental approach included for each biomass species, run in tripli-
cate, equaling 36 experiments in total with 2  2  2 full factorial design. Each reaction was
terminated by placing a 5 ml aliquot into cold water. After cooling, the pretreated biomass was
neutralized using 2N NaOH. The neutralized mixture was filtered through Whatman filter
paper-42 and keeps it under 6  C for sugar analysis.

C. Sugar analysis
Analysis of glucose production reported as total reducing sugars (TRS) was carried out
using the 3,5-dinitro salicylic acid (DNS) method. Two milliliter of appropriately diluted sam-
ple and 8 ml of DNS solution were placed into a sampling bottle. The mixture was then heated
up in boiling water for 5 min. Then, the sample was cooled to room temperature and a UV-Vis
spectrophotometer Cary 100 (Varian Co., Palo Alto, CA, USA) was used to measure its absorb-
ance. A blank solution consists of distilled water and DNS reagent was used to zero the spec-
trophotometer at 540 nm before analyzing the samples. A calibration curve was prepared by
determining the absorbance of standard glucose solutions of known concentrations. The glucose
concentration in the withdrawn sample was obtained by comparing the absorbance to the cali-
bration curve. The linear relationship between absorbance and concentration of an absorbing
species known as Beer-Lambert law was assumed applicable to the whole range of concentra-
tions (from 0 to 2.33 mol m3). The experimental results were fitted to a straight line by least
square method using EXCEL. The straight line fitted well the experimental data in the range con-
sidered with R2 value approaching one or at least 0.995, and the best fit equations were used in
subsequent analysis to determine the concentration of TRS for any measured value of absorb-
ance. About the determination of the reducer nature samples were taken during the hydrolysis.
It was proceeded in the same form as in the preceding paragraph, for the preparation of the cal-
ibration line, applying the analysis method to 1 ml sample of the hydrolyzed and doing the

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021201-4 Hernández et al. J. Renewable Sustainable Energy 4, 021201 (2012)

analysis by triplicate. Due to the relatively low specificity, one must run blanks diligently if the
colorimetric results are to be interpreted correctly and accurately. The rate of formation of these
soluble reducing sugars (i.e., glucose, cellobiose, and higher soluble oligodextrins) is taken as a
measure of the rate of lignocellulose hydrolysis,17–19 to finally represented as the percentage of
sugar recovery, defined as the weight of total reducing sugars found in the liquid divided by the
weight of cellulose and hemicellulose contained in the biomass.

D. Pretreatments
Pretreatment evaluated agents were two different classes each one containing two different
processes, and their characteristics were determined by each class with alkaline hydrolysis using
calcium sulfate and sodium hydroxide, water immersion for a certain time, and water auto-
claved at 121  C, taking into consideration high yields of biomass resemblances in acid hydro-
lysis. The experiment approach included for the biomass species, run in triplicate, equaling 30
experiments in total.
In the NaOH (delignification) and water (swelling) pretreatments, biomass was pretreated at
121  C in an autoclave. A total of 4 g of biomass sample and 40 ml of NaOH solution of 1%
were placed in a serum bottle and mixed using a glass rod, forming a slurry at a solid/liquid ratio
of 0.1 g/ml during an hour. All serum bottles were sealed and crimped before pretreatment.20,21
In the calcium sulfate (delignification) pretreatment, 0.10 g per gram of biomass dissolved
in distilled water, a certain amount of calcium sulfate remained insoluble, although this con-
tinued dissolving during pretreatment; biomass (4 g) was treated with 100 ml of the pretreat-
ment solution in 500 ml flasks in an orbital shaker agitated at 150 rpm at 60  C during 24 h
(Ref. 22). In order to produce swelling of the material, biomass samples were immersed in
water, using a liquid/solid ratio equal to 5/1, at room temperature for 1 h. After this time, the
material was washed three times with distilled water, filtered, and dried in an oven at 45  C
for 24 h (Ref. 11).

E. Statistical analysis
Results were subjected to the analysis of variance (ANOVA) using DESIGN-EXPERT software
version 8.06, Inc., Minneapolis, USA. The experimental data were fit using a low-order polyno-
mial equation to evaluate the effect of each independent variable (acid concentration and time)
to the response (% sugar recovery). In this study, a polynomial quadratic equation, as shown in
Eq. (1), was employed:
X X XX
y ¼ b0 þ bi Xi þ bii Xi2 þ bij Xi Xj ; (1)

where y is the response, xi and xj are independent variables, b0 is the offset term, bi are linear
coefficients, bii are quadratic coefficients, and bij are cross-product coefficients.

FIG. 1. Percent sugar recovery of sugarcane bagasse with dilute acid hydrolysis at different times and concentration of
acid (^ ¼ 1% w/w, h ¼ 2% w/w and D ¼ 5% w/w).

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021201-5 Cellulosic materials J. Renewable Sustainable Energy 4, 021201 (2012)

FIG. 2. Achieved percent of sugar recovery of sugarcane bagasse during dilute acid hydrolysis with 5% by weight of acid
subjected to different pretreatments (^ ¼ immersion in water for 24 h, h ¼ autoclaved water for 1 h, D ¼ autoclaved 1%
NaOH for 1 h, and ¼ alkaline hydrolysis).

III. RESULTS AND DISCUSSION


Acid hydrolysis of all cellulosic materials was performed using dilute H2SO4, as the most
widely used and tested approach. Cellulose and hemicellulose content of all biomass materials
was based upon the next references sugarcane bagasse,22 mango skin and mango bagasse,23 and
pine wood,5 which is used to calculate the percent of recovered sugars in the experiments. Fig. 1
shows the results of acid hydrolysis of sugarcane bagasse treated with H2SO4 at a concentration
of 1%-5% (w/w). An increase in the amount of acid solution from 1% to 5 % correlated with an
increased saccharification, with a maximum peak of 27.14% (5% acid—60 min) and a total accu-
mulated of sugar recovery of 20% to 25% higher than 1% and 2% acid concentration.
The experimental data shown in Fig. 1 were used to determine the regression coefficients
of the second-order polynomial equation using DESIGN-EXPERT software and the following models
that describe the percent sugar recovery in terms of actual parameter were obtained in the fol-
lowing equation:

% Sugar recovery ¼ 4:20793 þ 0:15296  Time þ 0:45746  Acid  0:002432  Time  Acid
 0:00039  Time2 þ 0:12000  Acid2 : (2)

To test the significance of the developed model as well as analyzing the effects of variables,
ANOVA was performed. A model is considered significant if its p-value (also known as the
Prob > F value) is lower than 0.05, indicating only a 5% chance that a “Model F-value” could
occur because of the noise. The Prob > F values were also used to evaluate the significance of

FIG. 3. Percent sugar recovery of mango skin with dilute acid hydrolysis at different times and concentration of acid
(^ ¼ 1% w/w, h ¼ 2% w/w, and D ¼ 5% w/w).

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021201-6 Hernández et al. J. Renewable Sustainable Energy 4, 021201 (2012)

FIG. 4. Achieved percent of sugar recovery of released of mango skin during dilute acid hydrolysis with 2% by weight of
acid subjected to different pretreatments (^ ¼ immersion in water for 24 h and h ¼ autoclaved water for 1 h).

the effects of each linear, quadratic, and interaction term on the response. Because the Prob > F
values for the model is low (less than 0.02), the model equation adequately describes the
response with 5 degrees of freedom.
Sugarcane bagasse was also hydrolyzed with dilute acid using a 5% by weight (because
with this concentration was obtained the maximum sugar recovery in the acid hydrolysis pro-
cess) and subjected to different pretreatments (immersion in water for 24 h, autoclaved water
for 1 h, autoclaved 1% NaOH for 1 h and alkaline hydrolysis) and the results are presented in
Fig. 2. All pretreatments presented a higher sugar recovery than just with the acid hydrolysis
process, and the maximum peak is presented with alkaline hydrolysis (56.62% at 120 min). Stat-
istically significant differences were determined by ANOVA when the pretreatments and sugar re-
covery were studied as an effect of the kind of pretreatment where the Prob > F values for the
model was 0.002, and statistically no significant differences were found.
Fig. 3 shows the results of acid hydrolysis of mango skin treated with H2SO4 at a concen-
tration of 1%-5% (w/w). Due to the material characteristics and composition differences com-
pared as such as sugarcane bagasse, the highest yield occurred within an acid concentration of
2%, with a maximum peak of 97.37% at 30 min. The equation that best describe the process
with the actual parameter is presented as follows:

% Sugar recovery ¼ 7:64965 þ 0:53169  Time þ 16:73778  Acid  0:00531  Time  Acid
 0:00012  Time2 þ 2:67535  Acid2 : (3)

FIG. 5. Percent sugar recovery of mango bagasse with dilute acid hydrolysis at different times and concentration of acid
(^ ¼ 1% w/w, h ¼ 2% w/w, and D ¼ 5% w/w).

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021201-7 Cellulosic materials J. Renewable Sustainable Energy 4, 021201 (2012)

FIG. 6. Percent sugar recovery of pine wood with dilute acid hydrolysis at different times and concentration of acid
(^ ¼ 1% w/w, h ¼ 2% w/w, and D ¼ 5% w/w).

This model with 5 degrees of freedom and a Prob > F values significant of 0.0242, with val-
ues for each model term, suggests that A, B, B2, C2, and AB are the model terms that have
significant effects on the percent of sugar recovery. However, the lack of fit test, which was
used to determine the adequacy of the model, indicates a not significant Prob > F value of
0.0833.
Mango skin was also hydrolyzed with dilute acid using a 2% by weight (because with this
concentration, the maximum yield in the acid hydrolysis process was obtained) and subjected to
different pretreatments (immersion in water for 24 h and autoclaved water for 1 h), and the
results are presented in Fig. 4. All pretreatments presented a lower sugar recovery compared
with those with only the acid hydrolysis process, and the maximum peak is presented with
immersion in water for 24 h (60.52% at 60 min). Besides no statistically significant differences
were found comparing the pretreatments with sugar recovery in the model with a low Prob > F
value (0.0486).
Acid hydrolysis of mango bagasse sugar recovery percent results are presented in Fig. 5
and presented a higher level of sugar recovery with a maximum peak of 202.91% (2% acid—
240 min), when compared to either mango skin and sugarcane bagasse (97.37% and 56.62%,
respectively). These results higher than the theoretical maximum could be explained with a
specific fraction of the material with lots of readily digestible sugars in the form of saccharose
or other sugars in which this material does not need a specific hydrolysis procedure and could
be fermented immediately. The mathematical model of the process is shown as follows:

% Sugar recovery ¼ 14:95652 þ 0:81545  Time þ 65:39142  Acid  0:02324  Time  Acid
 0:00228  Time2  12:23725  Acid 2 : (4)

Using 5 degrees of freedom, this model is described as not significant with a Prob > F value of
0.0710, with a lack of fit describe as well as not significant with a Prob > F value of 0.2384.
In Fig. 6, the sugar recovery (%) of acid hydrolysis process of pine wood is presented. It
can be noticed from Fig. 6 that acid concentration of 1% shows the best result compared to 2%
and 5% with a maximum peak occurred at 1% acid and 60 min (74.30% sugar recovery). The
mathematical model of the process is shown as follows:

% Sugar recovery ¼ 15:02568 þ 0:50983  Time þ 2:61101  Acid  0:01107  Time  Acid
 0:00151  Time2  0:14812  Acid2 : (5)

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021201-8 Hernández et al. J. Renewable Sustainable Energy 4, 021201 (2012)

FIG. 7. Achieved percent of sugar recovery of pine wood during dilute acid hydrolysis with 1% by weight of acid sub-
jected to different pretreatments (^ ¼ immersion in water for 24 h, h ¼ autoclaved water for 1 h, D ¼ autoclaved 1% NaOH
for 1 h, and ¼ alkaline hydrolysis).

Using 5 degrees of freedom, this model is described as significant with a Prob > F value of
0.0139, with a lack of fit described as well as not significant with a Prob > F value of 0.0893.
Pine wood was also hydrolyzed with dilute acid using a 1% by weight (because with this
concentration, the maximum yield in the acid hydrolysis process was obtained) and subjected to
different pretreatments (immersion in water for 24 h, autoclaved water for 1 h, autoclaved 1%
NaOH for 1 h and alkaline hydrolysis) and the results are presented in Fig. 7. All pretreatments
presented a higher sugar recovery (%) than just with the acid hydrolysis process, and the maxi-
mum peak is presented with autoclaved water for 1 h (82.36% at 60 min). No statistically signif-
icant differences were found by ANOVA when the pretreatments and sugar recovery were studied
as an effect of the kind of pretreatment used in the model with a Prob > F value of 0.007.
From all the studied materials, the pine wood was the one with minimum overall sugar re-
covery efficiency in both dilute acid hydrolysis and pretreatments processes lower than 60%;
besides just the mango bagasse was the only material that exceed the theoretical maximum,
even where there is a peak on the 200% probably due to readily digestible sugars that does not
need any pretreatment þ acid hydrolysis to obtain all the sugars from the cellulose-
hemicellulose fraction, which can subject this material immediately to a fermentation process.
Table I shows the approximate amount of theoretical production of ethanol in liters per ton
of each cellulosic material evaluated in this study. The maximum percent of sugar recovery
obtained in the experiments (sugarcane bagasse—56.62%, mango skin—97.37%, mango ba-
gasse—202.91%, and pine wood—82.36%) was used according to the preferred method.24 The
percent conversion is calculated by dividing the reducing sugars in solution by the theoretical
amount of sugars and multiplying by 100. The theoretical amounts of sugars are calculated
based upon the hemicellulose and cellulose content (dry basis).25

TABLE I. Theoretical ethanol production using highest experimental sugar recovery percent from cellulosic materials
(% in dry weight).

Sugarcane bagasse Mango skin Mango bagasse Pine wood

Amount of biomass (kg) 1000 1000 1000 1000


Cellulose þ hemicellulose content (kg) 664 563 649 616
Sugar conversion and recovery efficiency 0.5662 0.9737 2.0291 0.8236
Ethanol stoichiometric yield 0.51 0.51 0.51 0.51
Glucose fermentation efficiency 0.75 0.75 0.75 0.75
Ethanol yield from glucose (kg) 144 209 503 194
Total ethanol yield (liter) 165 241 579 223

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021201-9 Cellulosic materials J. Renewable Sustainable Energy 4, 021201 (2012)

IV. CONCLUSIONS
Mango (skin and bagasse), sugarcane bagasse, and pine wood are renewable, cheap, and
widely available resources. The hydrolysates obtained from all used biomass materials can be
used to produce hydrogen and methane by anaerobic fermentation process. Therefore, this study
can be conceived as the first stage of an integrated strategy for materials from the tropical
region utilization.
The data presented here supports the use of different tropical biomass materials for saccha-
rification processes to obtain valuable fermentation products. In particular, the use of mango
skin and bagasse waste residues from the fruit concentrate industry would provide an excellent
source of a cellulosic material easily hydrolyzed to a glucose rich, xylose sparse product, com-
parable to other biotechnologically important bioresources, like the ones also studied and well
known sugarcane bagasse and pine wood. In the present study, experimental data demonstrates
with the maximum percentage of sugar recovery from the conversion of sugarcane bagasse—
56.62% using alkaline hydrolysis, mango skin—97.37% using 2% dilute acid hydrolysis, mango
bagasse—202.91% using 2% dilute acid hydrolysis, and pine wood—82.36% by autoclaved
water treatment. It should be noted that mango bagasse from all the cellulosic material eval-
uated is the only one that does not need a pretreatment þ hydrolysis step to produce sugars
from lignocelluloses, because although it contains a specific fraction of fiber it also contains
another one with readily digestible sugars that can be taken directly into a fermentation process.
Besides, with a theoretical production of ethanol comparable with other common sources of
ethanol from the highest recovery from all biomass materials being sugarcane bagasse (165 l),
mango skin (241 l), mango bagasse (579 l), and pine wood (223 l).
The distribution of the corresponding cultivars is geographically distinctive, but their combined
distribution covers an important proportion of Mexican land as well in all the tropical region of the
word like India, Brazil, and China. Future studies should be proposed to employ techniques such as
HPLC/HPAEC to identify specific comprehensive sugars to developed kinetic measurements as
well as enzymes like Trichoderma reesei and Aspergillus niger; and finally going all through fer-
mentation experiments to obtain actual ethanol production measurements.
1
K. Stenberg, Ethanol from softwood: Process Development Based on Steam Pretreatment and SSF, 1st ed. (KFS AB,
Lund, Sweden, 1999), pp. 11–13, ISBN: 91-628-3583-1.
2
Z. Szengyel, Ethanol from Wood: Cellulase Enzyme Production, 1st ed. (KFS AB, Lund, Sweden, 2000), pp. 3–6.
3
C. Ajila and S. Bhat, J. Food Chem. 102, 1006 (2007), ISBN: 91-7874-039-8.
4
W. El-Zawawy and M. Ibrahim, J. Carbohydr. Polym. 84, 865 (2011).
5
N. S. Mosier and M. R. Ladisch, J. Biotechnol. Bioeng. 79, 610 (2002).
6
E. V. Canetierri and J. B. Silva, J. Ind. Eng. Chem. Res. 46, 1938 (2007).
7
K. Karimi and M. J. Taherzadeh, J. Biomass Bioenergy 30, 247 (2006).
8
X. Lu and Y. Zhang, Korean J. Chem. Eng. 25, 302 (2008).
9
A. Converti and M. Zilli, J. Chem. Eng. Technol. 23, 1013 (2000).
10
J. Hernandez-Salas and M. Villa-Ramirez, J. Bioresour. Technol. 100, 1238 (2009).
11
J. Ferrer and G. Paez, Rev. Fac. Agron. 19, 23 (2002), http://www.revfacagronluz.org.ve/PDF/enero_marzo2002/
ra1021%20abstract.pdf
12
M. Taherzadeh and Niklasson, J. Chem. Eng. Sci. 52, 2653 (1997).
13
N. Kosaric and A. Wieczorirek, Biotechnology: A Comprehensive Treatise (Verlag-Chemie, 1983), Vol. 3, pp. 257–285,
ISBN: 352-7257-640.
14
N. Aguilar-Rivera, Rev. Mex. Ing. Quı́m. 3, 257 (2004), http://redalyc.uaemex.mx/src/inicio/ArtPdfRed.jsp?iCve=
62030304
15
G. Urbaneja and J. R. Ferrer, Rev. Fac. Agron. 14, 265 (1997), http://www.revfacagronluz.org.ve/v14_2/v142z010.html
16
E. Varga and K. Réczey, J. Appl. Biochem. Biotech. 98–100, 73 (2002).
17
F. Carrillo, Structural Characterization of Lyocell Fibers and Its Behaviour towards Degradation Processes (Universitat
Politècnica de Catalunya, Barcelona, Spain, 2002).
18
P. Anantharam and V. Sasidhar, J. Biotechnol. Bioeng. 95, 904 (2006).
19
H. Ruofei and L. Lin, J. Biobased Mater. Bioeng. 2, 156 (2008).
20
J. Xu and J. J Cheng, J. Energy Fuels 24, 2113 (2010).
21
M. Taherzadeh and K. Karimi, Int. J. Mol. Sci. 9, 1621 (2008).
22
R. Sarita, J. Appl. Biochem. Biotechnol. 148, 45 (2008).
23
K. A. Pineda, “Enzymatic hydrolysis and characterization of mango skin and bagasse,” Bachelor’s thesis (Autonomous
University of Nayarit, Tepic, Mexico, 2011).
24
A. Demı́rbas , J. Energy Sources 27, 327 (2005).
25
E. C. Clausen and J. L. Gaddy, “Concentrated sulfuric acid process for converting lignocellulosic materials to sugars,”
U.S. patent 5,188,673 (1993).

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